JPH04342721A - Copolyester - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer, excellent in heat resistance and rubber-like elasticity and useful as thermoplastic elastomers, etc., by reacting a prescribed amount of a specific compound as a diol component of an aromatic polyester with a polylactone and a polycarbodiimide. CONSTITUTION:The objective copolymer is obtained by reacting (A) an aromatic polyester containing either of di- and monohydroxy compounds expressed by formulas I and II (R<1> to R<3> are alkylene; (p) is 3 or 4; (q) and (r) are 0 or 1; (l) is 2 or 3; (m) is 0 or 1] as a constituent component in an amount of 0.1-30mol% based on a diol component as part of the diol component mainly containing ethylene glycol and an acid component mainly containing terephthalic acid with (B) a polylactone such as epsilon-caprolactone and (C) a polycarbodimide such as poly(tolylcarbodiimide). Furthermore, the weight ratio of the components (A) and (B) is (30/70)-(70/30) and the component (C) is preferably added in an amount of 0.1-3wt.% based on the total amount of the components (A) and (B).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester copolymer useful as a thermoplastic elastomer, and more particularly to a polyester copolymer having rubber-like elasticity and excellent heat resistance.

0002

[Prior Art] Thermoplastic elastomers exhibit rubber-like properties such as rubber elasticity and low permanent set at room temperature, melt at high temperatures, and can be easily molded by injection molding, extrusion molding, or other molding methods normally used for plastics. It is a polymeric material that can be molded. These properties of thermoplastic elastomers are due to their characteristic molecular chain structure consisting of hard segments with strong intermolecular cohesion and flexible soft segments. That is, agglomeration between hard segments (crystals, hydrogen bonds,
(Van der Waals force) acts as a physical crosslinking point, resulting in the restraint of molecular chains. This constraint is maintained until the cohesion between the hard segments breaks. Therefore, thermoforming is possible at temperatures above that temperature. Demand for thermoplastic elastomers having such characteristics has increased significantly in recent years as a new polymer material that fills the gap between plastics (engineering plastics) and vulcanized rubber.

[0003] As a prior art related to a thermoplastic elastomer having an aromatic polyester as a hard segment and a lactone as a soft segment, Japanese Patent Publication No. 48-411
6, in which aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate and lactones are mixed in a ratio of 30/70 to 8.
A method for obtaining an elastic polyester block copolymer by reacting at a ratio of 0/20 (weight ratio) is described.

0004

[Problems to be Solved by the Invention] However, the polyester block copolymer disclosed in the above-mentioned publication has heat resistance and flexibility adjusted by the composition ratio of aromatic polyester and lactones. If an attempt is made to improve the flexibility, the flexibility decreases, and conversely, an attempt to improve the flexibility results in a decrease in heat resistance. In other words, when the composition ratio of aromatic polyester is increased to improve the heat resistance of a polyester copolymer, the rubber-like flexibility at around room temperature decreases, while the flexibility of the polyester copolymer is improved. Therefore, when the composition ratio of lactones is increased, the heat resistance decreases.

The present invention aims to solve the above-mentioned problems, and its purpose is to provide a polyester copolymer with excellent heat resistance and flexibility.

[0006]

[Means for Solving the Problems] The first invention provides an aromatic polyester whose constituent components are a diol component mainly containing ethylene glycol and an acid component mainly containing terephthalic acid;
A polyester copolymer obtained by reacting polylactone and polycarbodiimide, wherein the diol component of the aromatic polyester is represented by the following general formula [
I] and the dihydroxy compound represented by the following general formula [II
] is characterized in that at least one of the monohydroxy compounds represented by the above is used as a constituent component, and the hydroxy compound is contained in an amount of 0.1 mol% to 30 mol% of the diol component, thereby achieving the above-mentioned purpose. is achieved.

[0007]

[C3]

(In the formula, R1 and R2 independently represent an alkylene group, p is 3 or 4, and q and r are independently 0
or an integer greater than or equal to 1).

[0009]

[C4]

(In the formula, R3 represents an alkylene group, l is 2 or 3, and m is an integer of 0 or 1 or more)
.

[0011] The second invention also provides an aromatic polyester comprising a diol component mainly containing ethylene glycol and/or butylene glycol and an acid component mainly containing terephthalic acid, a lactone monomer, and a polycarbodiimide. A polyester copolymer obtained by reacting a dihydroxy compound represented by the general formula [I] according to claim 1 with a dihydroxy compound represented by the general formula [II] according to claim 1 as the diol component of the aromatic polyester. ]
It is characterized in that at least one of the monohydroxy compounds represented by the above is used as a constituent component, and the hydroxy compound is contained in an amount of 0.1 mol% to 30 mol% of the diol component, thereby achieving the above object. achieved.

Next, the present invention will be explained in detail.

First, the first invention will be explained.

The aromatic polyester used in the present invention is composed of a diol component mainly containing ethylene glycol and an acid component mainly containing terephthalic acid.

The dihydroxy compound used in the present invention is
It is represented by the above general formula [I] and is a low-molecular compound with a high melting point, and the alkylene groups R1 and R2 are preferably ethylene or propylene groups, and q and r are preferably 0 or 1. For example, 4,4''-dihydroxy-p-terphenyl, 4,4''-dihydroxy-p-quarterphenyl, 4,4''-di(2-hydroxyethoxy)-p-quarterphenyl, etc. Preferably used. The melting point of 4,4''-dihydroxy-p-terphenyl is 260°C, the melting point of 4,4'''-dihydroxy-p-quarterphenyl is 336°C, and the melting point of 4,4''-dihydroxy-p-terphenyl is 336°C; 2-hydroxyethoxy)-p
- The melting point of quarter phenyl is 403°C. In addition, 4
,4'''-dihydroxy-p-quarterphenyl is described, for example, in the Journal of Chemical
Society, 1379-85 (1940).

The dihydroxy compounds [I] may be used alone or in combination.

The dihydroxy compound [I] generally has high crystallinity, and as described above, it is a compound of 4,4''-dihydroxy-p-terphenyl, 4,4''-dihydroxy-p-terphenyl, 4,4''-dihydroxy-p-
-Quarterphenyl, 4,4'''-di(2-hydroxyethoxy)-p-quarterphenyl, etc. have high melting points, so when these dihydroxy compounds [I] are incorporated into the polymer chain, the polymer shows a peculiar property. That is, since the dihydroxy compound [I] exhibits crystallinity and has a high melting point, a strong and highly heat-resistant physical crosslink is formed even when the amount of the dihydroxy compound [I] is small. As a result, it is presumed that a thermoplastic elastomer with high heat resistance can be obtained without impairing the flexibility derived from the soft segment.

The monohydroxy compounds used in the present invention are represented by the general formula [II] and are rigid low-molecular compounds having a paraphenylene skeleton. Melting point is extremely high. Furthermore, it is known that the paraphenylene skeleton is effective as a mesogen for low-molecular liquid crystal compounds, and this means that the paraphenylene skeleton is effective not only in the solid state but also in the high temperature state (molten state).
This shows that it has strong cohesive force. Therefore, when the above-mentioned monohydroxy compound [II] is incorporated at the end of the polymer, very strong and highly heat-resistant physical crosslinking is produced, and a thermoplastic elastomer with excellent heat resistance is produced.

In the monohydroxy compound represented by the general formula [II], R3 is preferably an ethylene group or a propylene group, and m is preferably 0 or 1. Examples of the monohydroxy compound [II] include 4-hydroxy-p-terphenyl, 4-hydroxy-p-quarterphenyl, 4-(2-hydroxyethoxy)-
p-terphenyl, 4-(2-hydroxyethoxy)-
Examples include p-quarterphenyl. The monohydroxy compounds [II] may be used alone or in combination.

An aromatic polyester consisting of ethylene glycol, at least one of the dihydroxy compound [I] and monohydroxy compound [II], and terephthalic acid, a glycol other than ethylene glycol, a polyalkylene oxide, 2 Polysilicone having 2 or more hydroxyl groups, an aromatic diol component other than the above formulas [I] and [II], an aromatic dicarboxylic acid other than terephthalic acid, an aromatic hydroxycarboxylic acid, and an aliphatic dicarboxylic acid as constituent components. Although it may be included,
These are preferably 10 mol% or less of the total amount of the diol component and acid component.

[0021] As the above glycol, for example, 1,4
-butanediol, 1,3-butanediol, 1,3-
Propylene glycol, 1,5-pentanediol, 1
, 6-hexanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol,
1,10-decanediol, cyclopentane-1,2-
Diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4
-diol, cyclohexane-1,4-dimethanol, etc., which may be used alone or in combination of two or more.

[0022] Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide, etc., and these may be used alone or in combination of two or more. Good too. The number average molecular weight of the polyalkylene oxide is preferably 20,000 or less, more preferably 5,000 or less. If the number average molecular weight becomes too large, physical properties such as thermal stability of the aromatic polyester produced will deteriorate.

The above-mentioned polysilicone has two hydroxyl groups, and polysilicone with two hydroxyl groups at the ends of the molecule is preferable, such as dimethylpolysiloxane and diethylpolysiloxane, which have two hydroxyl groups at both ends of the molecule. Examples include siloxane and diphenylpolysiloxane. The number average molecular weight of the polysilicone is preferably 20,000 or less, more preferably 5,000 or less, since it becomes difficult to produce an aromatic polyester if it becomes large.

Examples of the aromatic diol include hydroquinone, resorcinol, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4
'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,
4'-dihydroxydiphenylmethane, bisphenol A, 1,1-di(4-hydroxyphenyl)cyclohexane, 1,2-bis(4-hydroxyphenoxy)ethane, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc. Can be mentioned.

Examples of the aromatic dicarboxylic acids include isophthalic acid, metal salts of 5-sulfoisophthalic acid, and 4,4'-
Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, 4,4'-dicarboxydiphenyl sulfone, 3,3'-dicarboxybenzophenone, 4,4'
Examples include -dicarboxybenzophenone, 1,2-bis(4-carboxyphenoxy)ethane, 1,4-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene.

The above-mentioned aromatic hydroxycarboxylic acids impart rigidity and liquid crystallinity to polyester, and include salicylic acid, metahydroxybenzoic acid, parahydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, and 3-bromo-benzoic acid. 4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid,
Examples include 3-phenyl-4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-4'-carboxybiphenyl, etc., and preferably parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-4'-carboxybiphenyl.

[0027] The aliphatic dicarboxylic acid has 10 carbon atoms.
The following are preferred, such as oxalic acid, malonic acid,
Examples include succinic acid, gludaric acid, adipic acid, suberic acid, and sebacic acid.

[0028] The aromatic polyester is composed of at least one hydroxy compound of the dihydroxy compound [I] and/or monohydroxy compound [II], ethylene glycol, and an acid mainly containing terephthalic acid.
When the content of dihydroxy compound [I] and/or monohydroxy compound [II] decreases, heat resistance decreases, and when the content increases, not only is it not possible to obtain a sufficient increase in molecular weight, but also the melting point increases, making it difficult to form the next molten ester. Since it cannot be subjected to the exchange step, the above dihydroxy compound [
I] and/or the monohydroxy compound [II] content is 0% of the diol component constituting the aromatic polyester.
．． 1 to 30 mol%, more preferably 0.5 to 20
It is mol%, more preferably 1.0 to 10 mol%. In addition, when polyalkylene oxide or polysilicone is used as a diol other than aromatic, the constituent unit thereof is counted as one monomer. That is, polyethylene oxide with a degree of polymerization of 10 is counted as 10 monomers. When dihydroxy compound [I] and monohydroxy compound [II] are used together, the ratio of dihydroxy compound [I] and monohydroxy compound [II] is 0<[II]/[I]+[II]<2 A range satisfying /3 is preferable.

[0029] The aromatic polyester comprising the above-mentioned components can be produced using any generally known polycondensation method. For example, ■ dicarboxylic acids and diol components (aliphatic diols, dihydroxy compounds,
(including monohydroxy compounds, etc.), ■ A method of reacting a lower ester of dicarboxylic acid with a diol component using transesterification,
■ A method of reacting a dicarboxylic acid halide and a diol component in a suitable solvent such as pyridine, ■ A method of reacting a metal alcoholate of a diol component with a dicarboxylic acid halide, ■ A method of reacting a dicarboxylic acid halide with a dicarboxylic acid A reaction method using transesterification,
Examples of methods include:

[0030] In the polycondensation, catalysts generally used in producing polyester may be used. This catalyst includes metals such as lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, etc. Examples thereof include organometallic compounds, organic acid salts, metal alkoxides, and metal oxides.

Particularly preferred catalysts are calcium acetate, diacyltinn, tetraacyltinn, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
These are tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyl titanate, germanium dioxide, and antimony trioxide. Two or more of these catalysts may be used in combination.

Furthermore, various stabilizers such as hindered phenol antioxidants and phosphorus stabilizers may be used to improve thermal stability during polymerization.

Examples of hindered phenolic antioxidants include triethylene glycol bis[3-(3-
t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3
-(3,5-dibutyl-4-hydroxyphenyl)propionate], tetrakis[methylene(3,5-di-t
-butyl-4-hydroxyhydrocinnamate)]methane, octadecyl-3-(3,5-di-t-butyl-
4-hydroxyphenyl)propionate, N,N'-
Hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5- Trimethyl-2,4,6-tris-(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-t-butyl-4-hydroxybenzylethyl)calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 3,9-bis[2-(3-(3
-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,
4,8,10-tetraoxaspiro[5.5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 2,2-bis[4
-(2-(3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy))ethoxyphenyl]propane, 2,6-di-t-butyl-4-methylphenol, and the like.

Examples of the above-mentioned phosphorus stabilizers include tris(nonylphenyl)phosphite, triisooctylphosphite, triisodecylphosphite, triphenylphosphite, diphenylisodecylphosphite, diphenylisooctylphosphite, Phosphite compounds such as phenylisodecyl phosphite, diisooctylphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite; distearylpentaerythritol di-phosphite, dioctylpentaerythritol di-phosphite Phosphite, diisodecylpentaerythritol-di-phosphite, bis(2,4
-di-t-butylphenyl)pentaerythritol-di-phosphite, bis(2,6-di-t-butyl-4-
pentaerythritol-di-phosphite compounds such as (methylphenyl) pentaerythritol-di-phosphite; tetrakis(2,4-di-t-butylphenyl)
Examples include -4,4'-biphenylene phosphonite.

[0035] Furthermore, in order to efficiently distill off water, alcohol, glycol, etc. produced as by-products during polymerization, it is preferable to reduce the pressure of the reaction system to 1 mmHg or less. The reaction temperature is generally 150-350°C.

The polylactone used in the present invention undergoes transesterification with the aromatic polyester to add an aliphatic chain, thereby imparting flexibility to the polyester copolymer. Polylactones obtained by ring-opening polymerization of lactone monomers having 4 or more carbon atoms in the ring are preferred, and polylactones obtained from 5- to 8-membered ring lactone monomers are more preferred. For example, ε-caprolactone, δ-valerolactone, γ-butyrolactone,
Examples include polylactones polymerized from enantolactone, caprylolactone, and the like. A polylactone composed of two or more types of lactone monomers may also be used.

[0037] Regarding the composition ratio of the aromatic polyester and polylactone, from the viewpoint of the elastic properties of the obtained polyester copolymer, the weight ratio of aromatic polyester/polylactone is preferably 30/70 to 80/20, and is particularly preferably in the range is 30/70 to 70/30.

The polycarbodiimide used in the present invention is a linear polycarbodiimide having an average of two or more carbodiimides per molecule. These carbodiimides may be aliphatic, alicyclic, or aromatic. For example, poly(tolylcarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(1,3,5-triisopropylphenylene-2,4 -carbodiimide). Two or more types of polycarbodiimides may be used in combination.

Further, the amount of polycarbodiimide added is 0.0 based on the total weight of aromatic polyester and polylactone.
It is preferably 5 to 5% by weight, more preferably 0.1 to 3% by weight.

[0040] Although the reaction with aromatic polyester, polylactone and polycarbodiimide proceeds without a catalyst,
The above catalysts may also be used. Further, at this time, the above-mentioned stabilizer may be added. When the reaction is carried out in a solvent-free system, the reaction temperature is usually a temperature at which the mixture of the aromatic polyester, polylactone and polycarbodiimide is uniformly melted, and a temperature higher than the melting point of the produced block copolymer. When aromatic polyester, polylactone and polycarbodiimide are reacted in a solvent system, an appropriate reaction temperature is selected. Generally, a range of 180°C to 300°C is preferred. If the temperature is lower than 180°C, it is difficult for the aromatic polyester to dissolve easily and uniformly with the polylactone, and if the temperature exceeds 300°C, decomposition and other undesirable side reactions occur. Further, when the above reaction is carried out using a solvent, the solvent must be a common solvent with aromatic polyester, polylactone and polycarbodiimide.

[0041] For this reaction, a polymerization apparatus normally used for polymerizing polyester is suitably used.

[0042] Furthermore, when reacting aromatic polyester, polylactone, and polycarbodiimide, usually all the components are added at the same time, but each component can also be added at different times until the reaction is completed. .

Further, the following additives may be added during or after the production of the polyester copolymer of the present invention within a range that does not impair practicality.

(i) Inorganic fiber: glass fiber, carbon fiber,
Boron fiber, silicon carbide fiber, alumina fiber, amorphous fiber, silicon/titanium/carbon fiber, etc.

(ii) Organic fibers: aramid fibers, etc.

(iii) Inorganic filler: calcium carbonate,
Titanium oxide, mica, talc, etc.

(iv) Flame retardants: hexabromocyclododecane, tris-(2,3-dichloropropyl) phosphate, pentabromophenyl allyl ether, etc.

(v) Ultraviolet absorber: p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2
'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone, etc.

(vi) Antioxidants: butylated hydroxyanisole, butylated hydroxytoluene, distearylthiodipropionate, dilaurylthiodipropionate, hindered phenolic antioxidants, etc.

(vii) Antistatic agent: N,N-bis(hydroxyethyl)alkylamine, alkylarylsulfonate, alkylsulfanate, etc.

(viii) Inorganic substances: barium sulfate, alumina, silicon oxide, etc.

(ix) Higher fatty acid salts: sodium stearate, barium stearate, sodium palmitate, etc.

(x) Other organic compounds: benzyl alcohol, benzophenone, etc.

(xi) Crystallization accelerator; highly crystallized polyethylene terephthalate, polytrans-cyclohexanedimethanol terephthalate, etc.

Furthermore, the obtained polyester copolymer is
Mixed with other thermoplastic resins, such as polyolefins, heavy polyolefins, polystyrenes, polyamides, polycarbonates, polysulfones, polyesters, etc.
Alternatively, it may be mixed with a rubber component to modify its properties.

Next, the second invention will be explained.

The aromatic polyester used in the present invention is composed of a diol component mainly containing ethylene glycol and/or butylene glycol and an acid component mainly containing terephthalic acid.

As butylene glycol, either 1,4-butanediol or 1,3-butanediol can be used. As diol components other than ethylene glycol and butylene glycol, dihydroxy compounds represented by the above general formula [I] and the above general formula [II]
Contains at least one of the monohydroxy compounds represented by:

The dihydroxy compound [I] is a low-molecular compound with a high melting point, and the alkylene groups R1 and R2 are preferably ethylene or propylene groups, and q and r are preferably 0 or 1. For example, the compounds described in the first invention are preferably used. Further, the dihydroxy compounds [I] may be used alone or in combination.

As explained in the first invention, when the dihydroxy compound [I] is incorporated into a polymer chain, the polymer exhibits unique properties. That is, since the dihydroxy compound [I] exhibits crystallinity and has a high melting point, a strong and highly heat-resistant physical crosslink is formed even when the amount of the dihydroxy compound [I] is small. As a result, it is presumed that a thermoplastic elastomer with high heat resistance can be obtained without impairing the flexibility derived from the soft segment.

The monohydroxy compounds represented by the general formula [II] are rigid, low-molecular compounds having a paraphenylene skeleton, and the melting points of these compounds are extremely high reflecting their characteristic molecular structures. Furthermore, the paraphenylene skeleton is known to be effective as a mesogen for low-molecular liquid crystal compounds, and this is because the skeleton has a strong cohesive force not only in the solid state but also in the high temperature state (molten state). This shows that. Therefore, when the above-mentioned monohydroxy compound [II] is incorporated at the end of the polymer, very strong and highly heat-resistant physical crosslinking is produced, and a thermoplastic elastomer with excellent heat resistance is produced.

In the monohydroxy compound represented by the general formula [II], R3 is preferably an ethylene group or a propylene group, and n is preferably 0 or 1. Examples of the monohydroxy compound include the compounds described in the first invention. Monohydroxy compound [II
] may be used alone or in combination.

[0063] At least one of ethylene glycol and butylene glycol, at least one of dihydroxy compound [I] and monohydroxy compound [II], and terephthalic acid are added to the aromatic polyester, and a fat other than the above is added. group glycol, polyalkylene oxide, polysilicone having two hydroxyl groups,
Aromatic diol components other than those of the general formulas [I] and [II], aromatic dicarboxylic acids other than terephthalic acid, aromatic hydroxycarboxylic acids, and aliphatic dicarboxylic acids may be contained as constituent components; When it is contained, it is preferably 10 mol % or less of the total amount of the diol component and acid component.

[0064] Examples of the aliphatic glycols include:
Examples include the compounds described in the first invention, and these may be used alone or in combination of two or more.

Examples of the above-mentioned polyalkylene oxides include the compounds described in the first invention, and these may be used alone or in combination of two or more. If the number average molecular weight of the polyalkylene oxide becomes small, the ability to impart flexibility to the aromatic polyester produced will decrease, and if it becomes too large, the physical properties such as thermal stability of the resulting aromatic polyester will decrease. ,00
It is preferably 0 or less, more preferably 5,000 or less.

The above-mentioned polysilicone has two hydroxyl groups, preferably a polysilicone in which the two hydroxyl groups are located at the ends of the molecule, such as the compounds described in the first invention. As the number average molecular weight of polysilicone increases, it becomes difficult to produce aromatic polyester.
20,000 or less is preferable, more preferably 5,000
It is less than or equal to 0.

Examples of the aromatic diol, aromatic dicarboxylic acid, and aromatic hydroxycarboxylic acid include the first
Examples include the compounds described in the invention.

The aliphatic dicarboxylic acid mentioned above is preferably a dicarboxylic acid having 10 or less carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, and sebacic acid.

[0069] An aromatic polyester consisting of at least one hydroxy compound among the dihydroxy compound [I] and monohydroxy compound [II], at least one of ethylene glycol and butylene glycol, and an acid mainly containing terephthalic acid. are dihydroxy compound [I] and monohydroxy compound [II]
When the content of dihydroxy compound [I] decreases, the heat resistance decreases, and when the content increases, not only a sufficient increase in molecular weight cannot be obtained, but also the melting point increases and it can no longer be used in the next melt transesterification step. ] and/or the monohydroxy compound [II] content is 0.1 to 30 mol% of the diol component constituting the aromatic polyester.
It is more preferably 0.5 to 20 mol%, and still more preferably 1.0 to 10 mol%. In addition, when polyalkylene oxide or polysilicone is used as a diol other than aromatic, the constituent unit thereof is counted as one monomer. That is, polyethylene oxide with a degree of polymerization of 10 is counted as 10 monomers. Dihydroxy compound [I
] and monohydroxy compound [II], the ratio of dihydroxy compound [I] and monohydroxy compound [II] is 0<[II]/[I]+[II]
A range satisfying <2/3 is preferable.

[0070] The aromatic polyester consisting of the above constituent components can be produced using the polycondensation method described in the first invention.

[0071] In the polycondensation, catalysts generally used in producing polyester may be used. Examples of this catalyst include those described in the first invention.

[0072] Two or more of these catalysts may also be used in combination.

Furthermore, various stabilizers such as hindered phenol antioxidants and phosphorus stabilizers may be used to improve thermal stability during polymerization.

In addition, in order to efficiently distill water, alcohol, glycol, etc. that are by-produced during polymerization and obtain a high molecular weight polymer, the reaction system should be controlled at 1 mmHg in the late stage of polymerization.
It is preferable to reduce the pressure to below. The reaction temperature is generally 15
The temperature is 0 to 350°C.

The lactone monomer used in the present invention is
Those that open the ring and react with an acid or hydroxyl group to add an aliphatic chain, and that have 4 or more carbon atoms in the ring are preferably used, and more preferably 5- to 8-membered rings. It is. Examples include ε-caprolactone, δ-valerolactone, γ-butyrolactone, enantolactone, caprylolactone, and the like. Two or more types of lactone monomers may be used in combination.

[0076] Regarding the composition ratio of the aromatic polyester and the lactone monomer, from the viewpoint of the elastic properties of the obtained polyester copolymer, the weight ratio of the aromatic polyester/lactone monomer is preferably 30/70 to 80/20, particularly The preferred range is 30/70 to 70/30.

The polycarbodiimide used in the present invention is a linear polycarbodiimide having an average of two or more carbodiimides per molecule. These carbodiimides may be aliphatic, alicyclic, or aromatic. For example, those described in the first invention can be mentioned.

The amount of polycarbodiimide added is 0.0 based on the total weight of aromatic polyester and polylactone.
It is preferably 5 to 5% by weight, more preferably 0.1 to 3% by weight.

The reaction between the aromatic polyester, lactone monomer and polycarbodiimide proceeds without a catalyst, but the above-mentioned catalysts may also be used. Further, at this time, the above-mentioned stabilizer may be added. When the reaction is carried out in a solvent-free system, the reaction temperature is usually a temperature at which the mixture of the aromatic polyester, lactone monomer and polycarbodiimide is uniformly melted, and a temperature higher than the melting point of the produced block copolymer. When reacting aromatic polyester, lactone monomer and polycarbodiimide in a solvent system,
The reaction temperature is appropriately selected. Generally 180℃~3
A range of 00°C is preferred. At temperatures below 180°C, it is difficult for aromatic polyester to dissolve easily and uniformly with polylactone;
When the temperature exceeds 00°C, decomposition and other undesirable side reactions occur. Further, when the above reaction is carried out using a solvent, the solvent must be a common solvent with the aromatic polyester, lactone monomer and polycarbodiimide.

[0080] For this reaction, a polymerization apparatus normally used for polymerizing polyester is suitably used.

[0081] Furthermore, when reacting aromatic polyester, lactone monomer and polycarbodiimide, usually all the components are added at the same time, but each component may be added at different times until the reaction is completed. can.

The additives described in the first aspect of the invention may be added during or after the production of the aromatic polyester of the present invention to the extent that practicality is not impaired.

The polyester copolymers of the first and second inventions have a segment having a paraphenylene skeleton (the above general formulas [I] and [II]) in their molecular chains, so that they are superior to conventional commercially available elastomers. It is a thermoplastic elastomer with extremely high heat resistance and excellent flexibility near room temperature, making it suitable for press molding, extrusion molding, injection molding,
A molded band is formed by a molding method such as blow molding. The physical properties of the molded product can be changed arbitrarily depending on its constituent components and their blending ratios, making it suitable for flexible molded products such as automobile parts, hoses, belts, and backings, as well as paints, adhesives, etc. be done.

[0084]

EXAMPLES The present invention will be explained below based on examples.

[0085] The physical properties of the polyester copolymers obtained in the following examples were measured according to the following method.

A No. 3 dumbbell test piece having a thickness of 2 mm was prepared by injection using a polyester copolymer in accordance with JIS K-6301. Using this dumbbell, the following physical properties were measured.

■Vicat softening point: JIS K-6301
Measured under a load of 1 kg.

■Tensile strength and elongation at break: 23
The test was conducted at a tensile strength of 50 mm/min at ℃.

Example 1 (A) Synthesis of 4,4'''-dihydroxy-p-quarterphenyl 4-hydroxy-4-bromobiphenyl 6
0.0g, 100g of methanol, 300g of 10wt% sodium hydroxide solution and 13g of palladium/carbon.
was added and reacted for 4 hours under conditions of 120°C and 5 atm to obtain disodium salt of 4,4'''-dihydroxy-p-quarterphenyl. N to this solid
．． After adding N-dimethylformamide and separating the catalyst by heating and filtration, the filtrate was precipitated with dilute sulfuric acid and washed with methanol to obtain 4,4'''-dihydroxy- as a white crystalline powder.
p-quarterphenyl (hereinafter abbreviated as DHQ) was obtained. The melting point of DHQ was 336°C.

(B) Aromatic polyester synthesis stirrer,
In a 1 liter glass flask equipped with a thermometer, gas inlet and distillation port, add 1 liter of dimethyl terephthalate.
94g (1.0mol), ethylene glycol 138g
(2.24 mol), and small amounts of calcium acetate and antimony trioxide were added as catalysts. After purging the inside of the flask with nitrogen, the inside of the flask was heated and reacted at 180° C. for 3 hours. Along with the reaction, methanol began to distill out from inside the flask, and bis(2-hydroxyethyl) terephthalate was obtained.

[0091] 10.14 g of the above DHQ was added to this flask.
(0.15 ml) was added, the temperature of the flask was raised to 280°C, and the reaction was carried out at this temperature for about 2 hours. Next, the distillation port was connected to a vacuum vessel, and the flask was reacted for 1 hour while the pressure inside the flask was reduced to 1 mmHg. During the reaction, ethylene glycol was distilled out, and an extremely viscous liquid was formed in the flask. After cooling the flask,
The glass flask was broken and the product was removed.

(C) Synthesis of polyester copolymer 250 g of the aromatic polyester obtained in (B) above and polylactone (U .CC TONE Polymer P-700: poly-ε-caprolactone; average molecular weight approximately 400) 250 g, polycarbodiimide (Sumitomo Bayer Stavaxol P-1)
00) 2g and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4
After 1.0 g of -hydroxybenzyl)benzene was charged and the inside of the flask was purged with nitrogen, it was heated to 260° C. in an oil bath with stirring. The reaction system became a homogeneous viscous polymer melt. Subsequently, the mixture was reacted for 1 hour under a nitrogen stream. The obtained polymer had a Vicat softening point (1 kg load) of 125° C., a Shore D hardness of 38, and good rubber-like elasticity. Also, the tensile strength at break is 250Kg/cm2
The tensile elongation at break was 1700%.

Example 2 (D) Synthesis of aromatic polyester 194 g (1.0 mol) of dimethyl terephthalate, 1. 202 g (2.24 mol) of 4-butylene glycol and small amounts of calcium acetate and tetrabutyl titanate as catalysts were added. After purging the inside of the flask with nitrogen, the inside of the flask was heated and reacted at 180° C. for 3 hours. Along with the reaction, methanol began to distill out from inside the flask, and bis(2-hydroxybutyl) terephthalate was obtained.

[0094] 10.14 g (0.15 ml) of DHQ synthesized in the same manner as in Example 1 was added to this flask, the temperature of the flask was raised to 270°C, and the reaction was carried out at this temperature for about 2 hours. Next, the distillation port was connected to a vacuum vessel, and the flask was reacted for 1 hour while the pressure inside the flask was reduced to 1 mmHg. During the reaction, butylene glycol was distilled out, and an extremely viscous liquid was formed in the flask. After the flask was allowed to cool, the glass flask was broken and the product was taken out.

(E) Synthesis of polyester copolymer 200 g of the aromatic polyester obtained in the above (D) and ε-caprolactone were placed in a 1 liter glass flask equipped with a stirring blade, a gas inlet, and a distillation port. 300g,
2 g of the same polycarbodiimide as in Example 1 and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) as a heat stabilizer.
After charging 1.0 g of benzene and purging the inside of the flask with nitrogen, it was heated to 240° C. in an oil bath while stirring. The reaction system became a homogeneous viscous polymer melt. Subsequently, the mixture was reacted for 1 hour under a nitrogen stream, and then the gas inlet was connected to a vacuum pump, and the reaction was continued for another 1 hour while the pressure inside the flask was reduced to 1 mmHg. The obtained polymer had a Vicat softening point (1 kg load) of 110° C., a Shore D hardness of 30, and good rubber-like elasticity. Further, the tensile strength at break was 220 Kg/cm2, and the tensile elongation at break was 1600%.

Example 3 DHQ was synthesized in the same manner as in Example 1, and then
An aromatic polyester was synthesized in the same manner.

(F) Synthesis of polyester copolymer 250 g of the aromatic polyester obtained in (B) above and ε-caprolactone were placed in a 1 liter glass flask equipped with a stirring blade, a gas inlet, and a distillation port. 250g,
2 g of the same polycarbodiimide as in Example 1 and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) as a heat stabilizer.
After charging 1.0 g of benzene and purging the inside of the flask with nitrogen, it was heated to 250° C. in an oil bath while stirring. The reaction system became a homogeneous viscous polymer melt. Subsequently, the mixture was reacted for 1 hour under a nitrogen stream, and then the gas inlet was connected to a vacuum pump, and the reaction was continued for another 1 hour while the pressure inside the flask was reduced to 1 mmHg. The obtained polymer had a Vicat softening point (1 kg load) of 130° C., a Shore D hardness of 37, and good rubber-like elasticity. Further, the tensile strength at break was 260 Kg/cm2, and the tensile elongation at break was 1800%.

[0098]

Effects of the Invention As is clear from the above explanation, the polyester copolymer of the present invention can provide a thermoplastic elastomer with excellent heat resistance, flexibility, and moldability, and can be used for various parts. It can be used suitably.

Claims (2)

[Claims] Claim 1: A polyester copolymer obtained by reacting an aromatic polyester whose constituent components are a diol component mainly containing ethylene glycol and an acid component mainly containing terephthalic acid, a polylactone, and a polycarbodiimide. As the diol component of the aromatic polyester, at least one of a dihydroxy compound represented by the following general formula [I] and a monohydroxy compound represented by the following general formula [II] is used as a constituent component; The hydroxy compound is 0.1 mol% to 30% of the diol component
A polyester copolymer characterized by containing mol%. [Formula 1] (wherein, R1 and R2 independently represent an alkylene group, and p
is 3 or 4, and q and r independently represent 0 or an integer of 1 or more). embedded image (wherein, R3 represents an alkylene group, l is 2 or 3, and m represents an integer of 0 or 1 or more). Claim 2: Obtained by reacting an aromatic polyester whose constituent components are a diol component mainly containing ethylene glycol and/or butylene glycol, an acid component mainly containing terephthalic acid, a lactone monomer, and a polycarbodiimide. A polyester copolymer comprising a dihydroxy compound represented by the general formula [I] according to claim 1 and a dihydroxy compound represented by the general formula [II] according to claim 1 as the diol component of the aromatic polyester. A polyester copolymer characterized in that at least one of the monohydroxy compounds is a constituent component, and the hydroxy compound is contained in an amount of 0.1 mol % to 30 mol % of the diol component.